Method of fabricating and servicing a photomask

ABSTRACT

A method includes placing a photomask having a contamination on a surface thereof in a plasma processing chamber. The contaminated photomask is plasma processed in the plasma processing chamber to remove the contamination from the surface. The plasma includes oxygen plasma or hydrogen plasma.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/738,003 filed Sep. 28, 2018, the entire disclosure of which isincorporated herein by reference.

BACKGROUND

As the semiconductor industry has progressed into nanometer technologyprocess nodes in pursuit of higher device density, higher performance,and lower costs, challenges from both fabrication and design issuesbecome greater. Technological advances in IC materials and design haveproduced generations of ICs where each generation has smaller and morecomplex circuits than the previous generation. In the course of ICevolution, functional density (i.e., the number of interconnecteddevices per chip area) has generally increased while geometry size(i.e., the smallest component (or line) that can be created using afabrication process) has decreased. This scaling down process generallyprovides benefits by increasing production efficiency and loweringassociated costs. Such scaling down has also increased the complexity ofprocessing and manufacturing ICs.

Photolithography operations are one of the key operations in thesemiconductor manufacturing process. Photolithography techniques includeultraviolet lithography, deep ultraviolet lithography, and extremeultraviolet lithography (EUVL). The photomask is an important componentin photolithography operations. It is critical to fabricate and maintainphotomasks free of resolvable defects. However, photomask fabricationtechniques typically include electron beam lithography and etchingoperations, which can generate particles and etching residues. Further,use of the photomask during photolithographic operations can generateparticle residue. For example, EUVL can generate contamination,including hydrocarbon particles during photoresist exposure operations.Heat generated during EUV exposure can cause partial decomposition andvolatilization of the photoresist. The decomposed and volatilizedresidues can contaminate the photomask. In addition, during long termmask storage the mask can be contaminated by particles and residue. Forexample, Van der Waals force resulting from the high concentration ofmetal atoms in an EUV photomask attracts contaminant particles. Thecontaminating particles and residue may include hydrocarbons.Hydrocarbon contamination may not be completely removed during maskcleaning operations. Hydrocarbon contamination may cause proximity andcritical dimension uniformity drift and white spot defects.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure is best understood from the following detaileddescription when read with the accompanying figures. It is emphasizedthat, in accordance with the standard practice in the industry, variousfeatures are not drawn to scale and are used for illustration purposesonly. In fact, the dimensions of the various features may be arbitrarilyincreased or reduced for clarity of discussion.

FIG. 1 shows an extreme ultraviolet lithography tool according to anembodiment of the disclosure.

FIG. 2 shows a schematic diagram of a detail of an extreme ultravioletlithography tool according to an embodiment of the disclosure.

FIG. 3 is a cross-sectional view of a reflective mask according toembodiments of the disclosure.

FIGS. 4A, 4B, 4C, 4D, 4E, 4F, 4G, and 4H schematically illustrate amethod of fabricating and cleaning a photomask according to anembodiment of the disclosure.

FIG. 5 is a flowchart illustrating a method of removing contaminationfrom a photomask according to an embodiment of the disclosure.

FIGS. 6A, 6B, 6C, 6D, 6E, 6F, 6G, 6H, and 6I schematically illustrate amethod of fabricating and cleaning a photomask according to anembodiment of the disclosure.

FIG. 7 is a flowchart illustrating a method of manufacturing a photomaskand removing contamination from the photomask according to an embodimentof the disclosure.

FIG. 8 is a flowchart illustrating a method of manufacturing and using aphotomask and removing contamination from the photomask according to anembodiment of the disclosure.

FIG. 9 is a flowchart illustrating a method of using a photomask andremoving contamination from the photomask according to an embodiment ofthe disclosure.

FIG. 10 is a flowchart illustrating a method of reducing white spotdefects and critical dimension uniformity drift according to anembodiment of the disclosure.

FIG. 11 is a flowchart illustrating a method of removing contaminationfrom a photomask according to an embodiment of the disclosure.

DETAILED DESCRIPTION

It is to be understood that the following disclosure provides manydifferent embodiments, or examples, for implementing different featuresof the disclosure. Specific embodiments or examples of components andarrangements are described below to simplify the present disclosure.These are, of course, merely examples and are not intended to belimiting. For example, dimensions of elements are not limited to thedisclosed range or values, but may depend upon process conditions and/ordesired properties of the device. Moreover, the formation of a firstfeature over or on a second feature in the description that follows mayinclude embodiments in which the first and second features are formed indirect contact, and may also include embodiments in which additionalfeatures may be formed interposing the first and second features, suchthat the first and second features may not be in direct contact. Variousfeatures may be arbitrarily drawn in different scales for simplicity andclarity.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The device may be otherwise oriented (rotated 90 degrees orat other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly. In addition, the term“made of” may mean either “comprising” or “consisting of.”

The present disclosure is generally related to extreme ultraviolet (EUV)lithography masks and methods. In an EUVL tool, a laser-produced plasma(LPP) generates extreme ultraviolet radiation which is used to image aphotoresist-coated substrate. In an EUV tool, an excitation laser heatsmetal (e.g., tin, lithium, etc.) target droplets in the LPP chamber toionize the droplets to plasma, which emits the EUV radiation. Forreproducible generation of EUV radiation, the target droplets arrivingat the focal point (also referred to herein as the “zone of excitation”)have to be substantially the same size and arrive at the zone ofexcitation at the same time as an excitation pulse from the excitationlaser arrives. Thus, stable generation of target droplets that travelfrom the target droplet generator to the zone of excitation at a uniform(or predictable) speed contributes to efficiency and stability of theLPP EUV radiation source.

FIG. 1 is a schematic view of an EUV lithography tool with a laserproduction plasma (LPP) based EUV radiation source, constructed inaccordance with some embodiments of the present disclosure. The EUVlithography system includes an EUV radiation source 100 to generate EUVradiation, an exposure device 200, such as a scanner, and an excitationlaser source 300. As shown in FIG. 1, in some embodiments, the EUVradiation source 100 and the exposure device 200 are installed on a mainfloor MF of a clean room, while the excitation laser source 300 isinstalled in a base floor BF located under the main floor. Each of theEUV radiation source 100 and the exposure device 200 are placed overpedestal plates PP1 and PP2 via dampers DP1 and DP2, respectively. TheEUV radiation source 100 and the exposure device 200 are coupled to eachother by a coupling mechanism, which may include a focusing unit.

The EUV lithography tool is designed to expose a resist layer by EUVlight (also interchangeably referred to herein as EUV radiation). Theresist layer is a material sensitive to the EUV light. The EUVlithography system employs the EUV radiation source 100 to generate EUVlight, such as EUV light having a wavelength ranging between about 1 nmand about 100 nm. In one particular example, the EUV radiation source100 generates an EUV light with a wavelength centered at about 13.5 nm.In the present embodiment, the EUV radiation source 100 utilizes amechanism of laser-produced plasma (LPP) to generate the EUV radiation.

The exposure device 200 includes various reflective optic components,such as convex/concave/flat mirrors, a mask holding mechanism includinga mask stage, and wafer holding mechanism. The EUV radiation EUVgenerated by the EUV radiation source 100 is guided by the reflectiveoptical components onto a photomask secured on the mask stage. In someembodiments, the mask stage includes an electrostatic chuck (e-chuck) tosecure the photomask.

FIG. 2 is a simplified schematic diagram of a detail of an extremeultraviolet lithography tool according to an embodiment of thedisclosure showing the exposure of a photoresist-coated substrate 210with a patterned beam of EUV light. The exposure device 200 is anintegrated circuit lithography tool such as a stepper, scanner, step andscan system, direct write system, device using a contact and/orproximity mask, etc., provided with one or more optics 205 a, 205 b, forexample, to illuminate a patterning optic 205 c, such as a photomask,with a beam of EUV light, to produce a patterned beam, and one or morereduction projection optics 205 d, 205 e, for projecting the patternedbeam onto the substrate 210. A mechanical assembly (not shown) may beprovided for generating a controlled relative movement between thesubstrate 210 and patterning optic 205 c. As further shown in FIG. 2,the EUVL tool includes an EUV light source 100 including an EUV lightradiator ZE emitting EUV light in a chamber 105 that is reflected by acollector 110 along a path into the exposure device 200 to irradiate thesubstrate 210.

As used herein, the term “optic” is meant to be broadly construed toinclude, and not necessarily be limited to, one or more components whichreflect and/or transmit and/or operate on incident light, and includes,but is not limited to, one or more lenses, windows, filters, wedges,prisms, grisms, gratings, transmission fibers, etalons, diffusers,homogenizers, detectors and other instrument components, apertures,axicons and mirrors including multi-layer mirrors, near-normal incidencemirrors, grazing incidence mirrors, specular reflectors, diffusereflectors and combinations thereof. Moreover, unless otherwisespecified, neither the term “optic”, as used herein, are meant to belimited to components which operate solely or to advantage within one ormore specific wavelength range(s) such as at the EUV output lightwavelength, the irradiation laser wavelength, a wavelength suitable formetrology or any other specific wavelength.

Because gas molecules absorb EUV light, the lithography system for theEUV lithography patterning is maintained in a vacuum or a-low pressureenvironment to avoid EUV intensity loss.

In the present disclosure, the terms mask, photomask, and reticle areused interchangeably. In the present embodiment, the patterning optic205 c shown in FIG. 3 is a reflective photomask. In an embodiment, thereflective reticle 205 c includes a substrate 30 with a suitablematerial, such as a low thermal expansion material or fused quartz, asshown in FIG. 3. In various examples, the material includes TiO₂ dopedSiO₂, or other suitable materials with low thermal expansion. In someembodiments, the low thermal expansion glass substrate transmits lightat visible wavelengths, a portion of the infrared wavelengths near thevisible spectrum (near-infrared), and a portion of the ultravioletwavelengths. In some embodiments, the low thermal expansion glasssubstrate absorbs extreme ultraviolet wavelengths and deep ultravioletwavelengths near the extreme ultraviolet.

The reflective reticle 205 c includes multiple reflective layers 35deposited on the substrate. The multiple reflective layers 35 includes aplurality of film pairs, such as molybdenum-silicon (Mo/Si) film pairs(e.g., a layer of molybdenum 39 above or below a layer of silicon 37 ineach film pair). Alternatively, the multiple reflective layers 35 mayinclude molybdenum-beryllium (Mo/Be) film pairs, or other suitablematerials that are configured to highly reflect the EUV light. In someembodiments, the Mo/Si multilayer stack 35 includes from about 30alternating layers each of silicon and molybdenum to about 60alternating layers each of silicon and molybdenum. In some embodiments,from about 35 to about 50 alternating layers each of silicon andmolybdenum are formed. In certain embodiments, there are about 40alternating layers each of silicon and molybdenum. In some embodiments,the silicon and molybdenum layers are formed by chemical vapordeposition (CVD), plasma-enhanced CVD (PECVD), atomic layer deposition(ALD), physical vapor deposition (PVD) (sputtering), or any othersuitable film forming method. Each layer of silicon and molybdenum isabout 2 nm to about 10 nm thick. In some embodiments, the layers ofsilicon and molybdenum are about the same thickness. In otherembodiments, the layers of silicon and molybdenum are differentthicknesses. In some embodiments, the thickness of each layer of siliconand molybdenum is about 3 nm to about 4 nm.

The mask 205 c may further include a capping layer 40, such as a layermade of ruthenium (Ru) for protection of the multilayer 35. The cappinglayer 40 is disposed over the Mo/Si multilayer 35. In some embodiments,the capping layer 40 is made of ruthenium having a thickness of fromabout 2 nm to about 10 nm. In certain embodiments, the thickness of thecapping layer 40 is from about 2 nm to about 4 nm. In some embodiments,the capping layer 40 is formed by chemical vapor deposition,plasma-enhanced chemical vapor deposition, atomic layer deposition,physical vapor deposition, or any other suitable film forming method.

The mask further includes an absorption (or absorber) layer 45. Theabsorber layer 45 is disposed over the capping layer 40 in someembodiments. The absorption layer 45 is patterned to define a layer ofan integrated circuit (IC). In some embodiments, the absorber layer 45is Ta-based material. In some embodiments, the absorber layer is made ofTaN, TaO, TaBN, or TaBO having a thickness from about 25 nm to about 100nm. In certain embodiments, the absorber layer 25 thickness ranges fromabout 50 nm to about 75 nm. In some embodiments, the absorber layer 25is formed by chemical vapor deposition, plasma-enhanced chemical vapordeposition, atomic layer deposition, physical vapor deposition, or anyother suitable film forming method.

In some embodiments, an antireflective layer (not shown) is optionallyformed over the absorber layer 45. The antireflective layer is made of asilicon oxide in some embodiments, and has a thickness of from about 2nm to about 10 nm. In some embodiments, the thickness of theantireflective layer is from about 3 nm to about 6 nm. In someembodiments, the antireflective layer is formed by chemical vapordeposition, plasma-enhanced chemical vapor deposition, atomic layerdeposition, physical vapor deposition, or any other suitable filmforming method.

EUV masks require very low surface roughness and must have no resolvabledefects.

The reflective mask 205 c includes a backside conductive layer 60 insome embodiments. In some embodiments, the conductive layer 60 is formedon a second main surface of the substrate 30 opposing the first mainsurface of the substrate 30 on which the Mo/Si multilayer 35 is formed.In some embodiments, the conductive layer 60 is made of chromium,chromium nitride, or TaB having a thickness of about 25 nm to about 150nm. In some embodiments, the conductive layer 60 has a thickness ofabout 70 nm to about 100 nm. In some embodiments, the conductive layer60 is formed by chemical vapor deposition, plasma-enhanced chemicalvapor deposition, atomic layer deposition, physical vapor deposition, orany other suitable film forming method.

In some embodiments, the reflective mask 205 c includes a border 65etched down to the substrate 30 surrounding the pattern 55, also knownas a black border 65, to define a circuit area to be imaged and aperipheral area not to be imaged. The black border reduces light leakagein some embodiments.

In various embodiments of the present disclosure, the photoresist-coatedsubstrate 210 is a semiconductor wafer, such as a silicon wafer or othertype of wafer to be patterned.

The EUVL tool further include other modules or is integrated with (orcoupled with) other modules in some embodiments.

As shown in FIG. 1, the EUV radiation source 100 includes a targetdroplet generator 115 and a LPP collector 110, enclosed by a chamber105. In some embodiments, the target droplet generator 115 includes areservoir to hold a source material and a nozzle 120 through whichtarget droplets DP of the source material are supplied into the chamber105.

In some embodiments, the target droplets DP are droplets of tin (Sn),lithium (Li), or an alloy of Sn and Li. In some embodiments, the targetdroplets DP each have a diameter in a range from about 10 microns (μm)to about 100 μm. For example, in an embodiment, the target droplets DPare tin droplets, having a diameter of about 10 μm to about 100 μm. Inother embodiments, the target droplets DP are tin droplets having adiameter of about 25 μm to about 50 μm. In some embodiments, the targetdroplets DP are supplied through the nozzle 120 at a rate in a rangefrom about 50 droplets per second (i.e., an ejection-frequency of about50 Hz) to about 50,000 droplets per second (i.e., an ejection-frequencyof about 50 kHz). In some embodiments, the target droplets DP aresupplied at an ejection-frequency of about 100 Hz to a about 25 kHz. Inother embodiments, the target droplets DP are supplied at an ejectionfrequency of about 500 Hz to about 10 kHz. The target droplets DP areejected through the nozzle 127 and into a zone of excitation ZE at aspeed in a range of about 10 meters per second (m/s) to about 100 m/s insome embodiments. In some embodiments, the target droplets DP have aspeed of about 10 m/s to about 75 m/s. In other embodiments, the targetdroplets have a speed of about 25 m/s to about 50 m/s.

Referring back to FIG. 1, an excitation laser LR2 generated by theexcitation laser source 300 is a pulse laser. The laser pulses LR2 aregenerated by the excitation laser source 300. The excitation lasersource 300 may include a laser generator 310, laser guide optics 320 anda focusing apparatus 330. In some embodiments, the laser source 310includes a carbon dioxide (CO₂) or a neodymium-doped yttrium aluminumgarnet (Nd:YAG) laser source with a wavelength in the infrared region ofthe electromagnetic spectrum. For example, the laser source 310 has awavelength of 9.4 μm or 10.6 μm, in an embodiment. The laser light LR1generated by the laser generator 300 is guided by the laser guide optics320 and focused into the excitation laser LR2 by the focusing apparatus330, and then introduced into the EUV radiation source 100.

In some embodiments, the excitation laser LR2 includes a pre-heat laserand a main laser. In such embodiments, the pre-heat laser pulse(interchangeably referred to herein as the “pre-pulse) is used to heat(or pre-heat) a given target droplet to create a low-density targetplume with multiple smaller droplets, which is subsequently heated (orreheated) by a pulse from the main laser, generating increased emissionof EUV light.

In various embodiments, the pre-heat laser pulses have a spot size about100 μm or less, and the main laser pulses have a spot size in a range ofabout 150 μm to about 300 μm. In some embodiments, the pre-heat laserand the main laser pulses have a pulse-duration in the range from about10 ns to about 50 ns, and a pulse-frequency in the range from about 1kHz to about 100 kHz. In various embodiments, the pre-heat laser and themain laser have an average power in the range from about 1 kilowatt (kW)to about 50 kW. The pulse-frequency of the excitation laser LR2 ismatched with the ejection-frequency of the target droplets DP in anembodiment.

The laser light LR2 is directed through windows (or lenses) into thezone of excitation ZE. The windows adopt a suitable materialsubstantially transparent to the laser beams. The generation of thepulse lasers is synchronized with the ejection of the target droplets DPthrough the nozzle 120. As the target droplets move through theexcitation zone, the pre-pulses heat the target droplets and transformthem into low-density target plumes. A delay between the pre-pulse andthe main pulse is controlled to allow the target plume to form and toexpand to an optimal size and geometry. In various embodiments, thepre-pulse and the main pulse have the same pulse-duration and peakpower. When the main pulse heats the target plume, a high-temperatureplasma is generated. The plasma emits EUV radiation EUV, which iscollected by the collector mirror 110. The collector 110 furtherreflects and focuses the EUV radiation for the lithography exposingprocesses performed through the exposure device 200. The droplet catcheris used for catching excessive target droplets. For example, some targetdroplets may be purposely missed by the laser pulses.

Referring back to FIG. 1, the collector 110 is designed with a propercoating material and shape to function as a mirror for EUV collection,reflection, and focusing. In some embodiments, the collector 110 isdesigned to have an ellipsoidal geometry. In some embodiments, thecoating material of the collector 100 is similar to the reflectivemultilayer of the EUV mask. In some examples, the coating material ofthe collector 110 includes an alternating stack of first and secondreflective layers (such as a plurality of Mo/Si film pairs) and mayfurther include a capping layer (such as Ru) coated on the ML tosubstantially reflect the EUV light. In some embodiments, the collector110 may further include a grating structure designed to effectivelyscatter the laser beam directed onto the collector 110. For example, asilicon nitride layer is coated on the collector 110 and is patterned tohave a grating pattern.

In such an EUV radiation source, the plasma caused by the laserapplication creates physical debris, such as ions, gases, and atoms ofthe droplet, as well as the desired EUV radiation. It is necessary toprevent the accumulation of material on the collector 110 and also toprevent physical debris exiting the chamber 105 and entering theexposure device 200.

As shown in FIG. 1, in the present embodiment, a buffer gas is suppliedfrom a first buffer gas supply 130 through the aperture in collector 110by which the pulse laser is delivered to the tin droplets. In someembodiments, the buffer gas is H₂, He, Ar, N₂, or another inert gas. Incertain embodiments, H₂ used as H radicals generated by ionization ofthe buffer gas can be used for cleaning purposes. The buffer gas canalso be provided through one or more second buffer gas supplies 135toward the collector 110 and/or around the edges of the collector 110.Further, the chamber 105 includes one or more gas outlets 140 so thatthe buffer gas is exhausted outside the chamber 105.

Hydrogen gas has low absorption to the EUV radiation. Hydrogen gasreaching the coating surface of the collector 110 reacts chemically witha metal of the droplet forming a hydride, e.g., metal hydride. When tin(Sn) is used as the droplet, stannane (SnH₄), which is a gaseousbyproduct of the EUV generation process, is formed. The gaseous SnH₄ isthen pumped out through the outlet 140.

FIGS. 4A-4H schematically illustrate a method of fabricating andcleaning an EUV photomask 205 c for use in extreme ultravioletlithography (EUVL). EUVL employs scanners using light in the extremeultraviolet (EUV) region, having a wavelength of about 1 nm to about 100nm. The mask is a critical component of an EUVL system. EUV masks areusually reflective masks.

The photomask 205 c is formed from a photomask blank 20 including: thesubstrate 30, multilayer 35, capping layer 40, absorber layer 45, andconductive layer 60. As shown in FIG. 4A, a hard mask layer 50 is formedover the absorber layer 45 in some embodiments. The hard mask layer 50is formed over the antireflective layer in some embodiments. In someembodiments, the hard mask layer 50 is made of silicon, a silicon-basedcompound, chromium, or a chromium-based compound having a thickness ofabout 4 nm to about 20 nm. In some embodiments, the chromium-basedcompound includes CrON. In some embodiments, the hard mask layer 50 isformed by chemical vapor deposition, plasma-enhanced chemical vapordeposition, atomic layer deposition, physical vapor deposition, or anyother suitable film forming method.

A photoresist layer 75 is subsequently formed over the hard mask layer50, and the photoresist layer 75 is selectively exposed to actinicradiation. The photoresist layer 75 is a photosensitive layer that ispatterned by exposure to actinic radiation. Typically, the chemicalproperties of the photoresist regions struck by incident radiationchange in a manner that depends on the type of photoresist used. Thephotoresist layers 75 are either positive tone resists or negative toneresists. A positive tone resist refers to a photoresist material thatwhen exposed to radiation (typically UV light) becomes soluble in adeveloper, while the region of the photoresist that is non-exposed (orexposed less) is insoluble in the developer. A negative tone resist, onthe other hand, conventionally refers to a photoresist material thatwhen exposed to radiation becomes insoluble in the developer, while theregion of the photoresist that is non-exposed (or exposed less) issoluble in the developer. The region of a negative tone resist thatbecomes insoluble upon exposure to radiation may become insoluble due toa cross-linking reaction caused by the exposure to radiation.

The selectively exposed photoresist layer 75 is developed to form apattern 55′ in the photoresist layer 75. In some embodiments, theactinic radiation is an electron beam or an ion beam. In someembodiments, the pattern 55 corresponds to a pattern of semiconductordevice features for which the photomask 205 c will be used to form insubsequent operations. Whether a resist is a positive tone or negativetone may depend on the type of developer used to develop the resist. Forexample, some positive tone photoresists provide a positive pattern,(i.e.—the exposed regions are removed by the developer), when thedeveloper is an aqueous-based developer, such as a tetramethylammoniumhydroxide (TMAH) solution. On the other hand, the same photoresistprovides a negative pattern (i.e.—the unexposed regions are removed bythe developer) when the developer is an organic solvent. Further, insome negative tone photoresists developed with the TMAH solution, theunexposed regions of the photoresist are removed by the TMAH, and theexposed regions of the photoresist, that undergo cross-linking uponexposure to actinic radiation, remain on the substrate afterdevelopment.

Next, the pattern 55′ in the photoresist layer 75 is extended into thehard mask layer 50 forming a pattern 55″ in the hard mask layer 50exposing portions of the absorber layer 45, as shown in FIG. 4B. Thepattern 55″ extended into the hard mask layer 50 is formed by etching,in some embodiments, using a suitable wet or dry etchant that isselective to the hard mask layer 50.

Then, the pattern 55″ in the hard mask layer 50 is extended into theabsorber layer 45 forming a pattern 55′ in the absorber layer 45exposing portions of the capping layer 40, as shown in FIG. 4C. Thepattern 55′″ extended into the absorber layer 45 is formed by etching,in some embodiments, using a suitable wet or dry etchant that isselective to the absorber layer 45. In some embodiments, the cappinglayer 40 functions as an etch-stop layer. The photoresist layer 75 isremoved by a suitable photoresist stripper or oxygen plasma ashingoperation to expose the upper surface of the hard mask layer 50.

As shown in FIG. 4D, a second photoresist layer 85 is formed over theabsorber layer 45 filling the pattern 55 in the absorber layer afterremoving the hard mask layer 50. The hard mask layer is removed byetching using an etchant selective to the hard mask layer. The secondphotoresist layer 85 is selectively exposed to actinic radiation. Theselectively exposed second photoresist layer 85 is developed to form apattern 65′ in the second photoresist layer 85, as shown in FIG. 4D.

Next, the pattern 65′ in the second photoresist layer 85 is extendedinto the absorber layer 55, capping layer 40, and Mo/Si multilayer 35forming a pattern 65″ in the absorber layer 45, capping layer 40, andMo/Si multilayer 35 exposing portions of the substrate 30, as shown inFIG. 4E. The pattern 65″ is formed by etching, in some embodiments,using one or more suitable wet or dry etchants that are selective toeach of the layers that are etched.

In some embodiments, the second photoresist layer 85 is removed by asuitable photoresist stripper or an oxygen plasma ashing operation toexpose the upper surface of the absorber layer 45. The pattern 65 in theabsorber layer 45, capping layer 40, and the Mo/Si multilayer 35 definesa black border of the photomask 205 c in some embodiments of thedisclosure, as shown in FIG. 4F. After removal of the second photoresistlayer, the photomask 205 c undergoes a cleaning operation, inspection,and the photomask 205 c is repaired as necessary, to provide a finishedphotomask 205 c. In some embodiments, the black border 65 is formedfirst and then the semiconductor device pattern 55 is formed.

During the photomask manufacture or subsequent processing using thefinished photomask 205 c, including EUV exposures of photoresist-coatedsubstrates using the photomask, carbon-based residue, includinghydrocarbon contamination 95 is formed on pattern 55 in the absorberlayer. The contamination can be created by heat generated during EUVexposure that causes partial decomposition and volatilization of thephotoresist. The decomposed and volatilized residues can contaminate thephotomask. In addition, during long term mask storage the mask can becontaminated by particles and residue that become attached to the maskby Van der Waals forces. Hydrocarbon contamination 95 may adverselyaffect the performance of the photomask 205 c, including causingproximity and critical dimension uniformity drift, and white spotdefects. The thickness of the carbon residue over the mask pattern 55,increases the mask pattern dimensions to change and thereby causing achange in the critical dimension of patterns subsequently formed in aphotoresist layer. Therefore, after prolonged use or storage, theperformance of the photomask 205 c declines.

To restore the performance of the photomask 205 c and maintain theproximity and critical dimension of patterns formed by the photomask 205c, periodic maintenance of the photomask 205 c is performed in someembodiments of the disclosure. For example, as shown in FIG. 4H, acarbon-based residue (i.e.—hydrocarbon) removal operation is performed.In some embodiments, dry etching, including plasma etching, (aclean-flash or “c-flash” operation) is performed on the photomask. Insome embodiments, the oxygen or hydrogen plasma is applied to thecarbon-residue contaminated photomask to remove the carbon-residuecontamination. In some embodiments, oxygen plasma is applied to thecontaminated photomask and the hydrocarbon is removed according to thefollowing reaction: C_(m)H_(n)+O→H₂O+CO₂ (or CO if incompleteoxidation). In other embodiments, hydrogen plasma is applied to thecontaminated photomask and the hydrocarbon is removed according to thefollowing reaction: C_(m)H_(n)+H→CH₄+H₂. In both the oxygen plasma andhydrogen plasma embodiments, the reaction products are gases that areevacuated from the plasma reaction chamber.

FIG. 5 is a flowchart illustrating a method 400 of removingcontamination from a photomask according to an embodiment of thedisclosure. In operation S410, a photoresist-coated substrate is exposedto actinic radiation reflected off of a reflective photomask 205 c. Inoperation S420, a reflective photomask 205 c is stored for a period oftime without using the reflective photomask in a photolithographicoperation. Contamination forms on a surface of the reflective photomaskduring the exposing or storing. After either operation S410 or operationS420, the reflective photomask having contamination on a surface thereofis placed in a plasma processing chamber in operation S430. Thecontaminated reflective photomask is plasma processed (c-flash) in theplasma processing chamber to remove the contamination from the surfacein operation S440. The plasma includes oxygen plasma or hydrogen plasma.In some embodiments, chlorine is supplied to the plasma processingchamber during the plasma process in operation S450. In someembodiments, nitrogen is supplied to the plasma processing chamberduring the plasma process in operation S470. In some embodiments, heliumor argon are supplied to the plasma processing chamber during the plasmaprocess in operation S470. In some embodiments, the reflective photomask205 c is inspected in operation S480 to determine whether thecontamination is removed.

In some embodiments, the photomask 205 c is inspected using visualtechniques. The visual techniques may include using transmissionelectron microscopy (TEM) to image the surface of the mask. In someembodiments, energy-dispersive X-ray spectroscopy (EDS) is used alongwith TEM to map the distribution of carbon-residue contaminants on thephotomask. Because hydrocarbons absorb infrared radiation, infraredanalysis techniques are used to inspect the surface of the mask in someembodiments. In some embodiments, critical dimension uniformity drift,proximity drift, or white spot defects are monitored in the patternsformed on the photoresist-coated substrates, and when the criticaldimension uniformity drift, proximity drift, or the number of white spotdefects exceed a threshold value, the photomask is subjected to theplasma contamination removal processes (c-flash) described herein.

In some embodiments, contaminant removal from the surface of thephotomask using the plasma process (c-flash) according to the disclosureis performed after about 100 to about 2500 or more exposures (or shots)of photoresist-coated substrates to actinic radiation using thephotomask. In some embodiments, the contaminant removal using the plasmaprocess according to the disclosure is performed after about 2000 ormore exposures (shots) of photoresist-coated substrates using thephotomask. In some embodiments, the contaminant removal is performedafter about 1000 or more exposures (shots) of photoresist-coatedsubstrates using the photomask.

In some embodiments, proximity bias drift or critical dimensionuniformity drift, or white spot defects are monitored, and thecontaminant removal using plasma process according to the disclosure isperformed when the proximity bias drift, critical dimension uniformitydrift, or white spot defects exceed a certain threshold value.

FIGS. 6A-6I schematically illustrate a method of fabricating andcleaning a photomask 205 c. The operations in FIGS. 6A-6F of fabricatingthe photomask are the same as the operations in FIGS. 4A-4F. Thecontamination of the pattern layer 55 in the absorber layer occursduring storage of the photomask in a photomask pod 90. During long termmask storage, the mask can be contaminated by particles and residue thatbecome attached to the mask by Van der Waals forces. In this embodiment,the contaminants 95, shown in FIG. 6H, that attach to the surface of themask during storage (FIG. 6G) are also carbon-based residue(i.e.—hydrocarbon), as explained in reference to FIG. 4G. Thus, thecontamination is removed in FIG. 6I in the same manner as discussed withreference to FIG. 4H. In some embodiments, the photomask 205 c is storedin the photomask pod 90 for more than 30 days prior to the plasmacontaminant removal operations of the disclosure. In some embodiments,the photomask 205 c is stored for about 30 days to about 180 days in thephotomask pod 90 prior to the plasma contaminant operation of thedisclosure.

FIG. 7 is a flowchart illustrating a method 500, including an operationS510 of forming a photomask 205 c. The photomask 205 c is stored in aphotomask pod 90 in operation S520. In some embodiments, the photomaskis stored for about 30 days or more in the photomask pod 90. Afterremoving the photomask 205 c from the photomask pod 90, the photomask205 c is plasma processed in a plasma processing chamber in operationS530 to remove contamination 95 from a surface of the photomask 205 c.The plasma includes oxygen plasma or hydrogen plasma. In someembodiments, chlorine is supplied to the plasma processing chamberduring the plasma process in operation S540. In some embodiments,nitrogen is supplied to the plasma processing chamber during the plasmaprocess in operation S550. In some embodiments, helium or argon aresupplied to the plasma processing chamber during the plasma process inoperation S560.

In some embodiments, during the plasma removal of the carbon-basedresidues the source power of the plasma source ranges from about 100 Wto about 1000 W for embodiments 1 to 7. The bias power is about 0 W. Thepressure in the plasma processing chamber ranges from about 1 mtorr toabout 5 mtorr. The flow rate of oxygen in the plasma processing chamberranges from about 0 sccm to about 100 sccm. The flow rate of hydrogen inthe plasma processing chamber ranges from about 0 sccm to about 300sccm. A flow rate of nitrogen ranges from about 0 sccm to about 50 sccm.Chlorine is supplied to the plasma processing chamber at a flow rate ofabout 20 sccm to about 100 sccm. He or Ar are supplied to the plasmaprocessing chamber at a flow rate of about 0 sccm to about 300 sccm. Theplasma is applied to the contaminated photomask for a duration of about5 s to about 100 s. In some embodiments, the power applied to thechamber is RF power, such as 13.6 KHz RF power.

In some embodiments, the source power applied to the chamber ranges fromabout 200 W to about 800 W. In some embodiments, the source powerapplied to the chamber ranges from about 400 W to about 600 W. In someembodiments, oxygen is applied to the chamber at a flowrate of about 10sccm to about 100 sccm. In some embodiments, oxygen is applied to thechamber at a flowrate of about 20 sccm to about 80 sccm. In someembodiments, hydrogen is applied to the chamber at a flowrate of about20 sccm to about 100 sccm. In some embodiments, hydrogen is applied tothe chamber at a flowrate of about 30 sccm to about 80 sccm. In someembodiments, nitrogen is applied to the chamber at a flowrate of about10 sccm to about 50 sccm. In some embodiments, nitrogen is applied tothe chamber at a flowrate of about 20 sccm to about 40 sccm. In someembodiments, chlorine is applied to the chamber at a flowrate of about20 sccm to about 100 sccm. In some embodiments, chlorine is applied tothe chamber at a flowrate of about 40 sccm to about 80 sccm. In someembodiments, helium or argon are applied to the chamber at a flowrate ofabout 60 sccm to about 300 sccm. In some embodiments, helium or argonare applied to the chamber at a flowrate of about 100 sccm to about 250sccm. In some embodiments, the plasma is applied to the photomask forabout 20 s to about 80 s. In some embodiments, the plasma applied to thephotomask for about 30 s to about 70 s.

In some embodiments, oxygen and chlorine are the only gases supplied tothe chamber. In some embodiments, oxygen and nitrogen are the only gasessupplied to the chamber. In some embodiments, oxygen and helium are theonly gases supplied to the chamber. In some embodiments, oxygen andargon are the only gases supplied to the chamber. In some embodiments,hydrogen is the only gas supplied to the chamber. In some embodiments,hydrogen and helium are the only gases supplied to the chamber. In someembodiments, hydrogen and argon are the only gases supplied to thechamber.

In some embodiments, oxygen has a higher carbon residue removal ratethan hydrogen, which has a higher carbon removal rate than argon andhelium. However, the higher the carbon removal rate of the gas also canresult in Ru capping layer damage if the c-flash cleaning treatment timeis not adequately monitored. Once the carbon residue is removed, theplasma should be turned off to avoid damage to the mask.

FIG. 8 is a flowchart illustrating a method 600 according to anembodiment of the disclosure. In operation S610, a photomask 205 c isformed. In some embodiments, forming the photomask includes forming themultilayer, capping layer, and absorber layer over the substrate, andthen patterning the absorber layer to form the mask pattern. Thephotomask 205 c is used in a photolithographic process in operation S620to form a photoresist pattern on a substrate. In some embodiments, thephotomask 205 c is used for 1000 or more exposures (or shots). In someembodiments, the photomask 205 c is used for 2000 or more exposures(shots). After a number of exposures (shots), the photomask 205 c isplasma processed in a plasma processing or cleaning chamber in operationS630 to remove contamination from a surface of the photomask. The plasmaincludes oxygen plasma or hydrogen plasma. In some embodiments, chlorineis supplied to the plasma processing chamber during the plasma processin operation S640. In some embodiments, nitrogen is supplied to theplasma processing chamber during the plasma process in operation S650.In some embodiments, helium or argon are supplied to the plasmaprocessing chamber during the plasma process in operation S660.

FIG. 9 is a flowchart illustrating a method 700 according to anembodiment of the disclosure. In operation S710, a photoresist-coatedsubstrate is exposed to actinic radiation reflected off of a reflectivephotomask 205 c. After a number of exposures (shots), the reflectivephotomask 205 c is placed in a chamber, such as a cleaning chamber, inoperation S720. The reflective photomask 205 c is exposed to a plasma inthe chamber in operation S730 to remove contamination from a surface ofthe photomask. The plasma includes oxygen plasma or hydrogen plasma.

FIG. 10 is a flowchart illustrating a method 800 or reducing white spotdefects and critical dimension uniformity drift according to anembodiment of the disclosure. In operation S810, a photoresist-coatedsubstrate is exposed to actinic radiation reflected off of a reflectivephotomask 205 c. In operation S820, a reflective photomask 205 c isstored for a period of time without using the reflective photomask in aphotolithographic operation. After either operation S810 or operationS820, the reflective photomask 205 c is placed in a chamber in operationS830. Carbon-based residue contamination is removed from the surface ofthe reflective photomask 205 c using a plasma in operation S840. In someembodiments, the reflective photomask 205 c is inspected in operationS850 to determine whether the carbon-based residue contamination isremoved.

FIG. 11 is a flowchart illustrating a method 900 according to anembodiment of the disclosure. In operation S910, it is determinedwhether a surface of a photomask 205 c is contaminated with acarbon-based residue. The photomask 205 c is placed in a chamber inoperation S920 when it is determined the photomask 205 c is contaminatedwith the carbon-based residue. In some embodiments, the photomask 205 cis placed in the chamber when the amount of carbon-residue contaminationreaches a threshold amount. In operation S930, the photomask is exposedto a plasma to remove the carbon-based residue. After the exposure toplasma, it is determined in operation S940 whether the carbon residuecontamination is removed. When the carbon residue contamination isremoved in operation S940, the photomask 205 c is used in someembodiments to expose a photoresist-coated substrate to extremeultraviolet radiation in operation S950. In some embodiments, chlorine,nitrogen, helium, or argon are supplied to the chamber during theexposing the photomask to plasma in operation S960.

In some embodiments, the determination of whether the surface of thephotomask is contaminated with carbon-based residue and thedetermination of whether the carbon-based residue is removed is achievedby inspecting the surface of the photomask. In some embodiments, theinspection is performed using visual techniques. The visual techniquesmay include using transmission electron microscopy (TEM) to image thesurface of the mask. In some embodiments, energy-dispersive X-rayspectroscopy (EDS) is used along with TEM to map the distribution ofcarbon-residue contaminants on the photomask. In some embodiments,infrared analysis techniques are used. In other embodiments, criticaldimension uniformity drift, proximity drift, or white spot defects aremonitored in the patterns formed on the photoresist-coated substrates,and when the critical dimension uniformity drift, proximity drift, orthe number of white spot defects exceed a threshold value, the photomaskis subjected to the plasma contamination removal processes describedherein.

Photomasks subjected to the plasma removal (c-flash) of carbon-basedresidue according to embodiments of the disclosure have improvedproximity and critical dimension uniformity. In addition, methodsaccording to the present disclosure reduces white spot defects on EUVphotomasks. The methods of the present disclosure, therefore, providesharper, higher contrast patterned features than patterned featuresformed using photomasks that are not subjected to the plasma removaloperations of the present disclosure.

In some embodiments, performing hydrocarbon contamination removalaccording to the present disclosure improves the critical dimensionuniformity. In some embodiments, an improvement of about 50% or more ofthe standard deviation of the critical dimension uniformity is achievedover the use of photomasks that do not undergo the hydrocarboncontamination removal according to embodiments of the disclosure. Insome embodiments, the standard deviation of the critical dimensionuniformity of patterns formed by photomasks after about 2000 exposureswithout performing the hydrocarbon removal operation (c-flash) of thepresent disclosure is about 0.63, and the standard deviation of thecritical dimension uniformity of patterns formed by photomasks afterabout 2000 exposures and the hydrocarbon removal operation of thepresent disclosure is about 0.34.

In some embodiments, after the plasma processing, the center to edgedifference of the proximity drift across the photomask is reduced toabout 0.1 nm or less. In some embodiments, after the plasma processing,the proximity drift is restored to about 0.1 nm of the initial value ofthe photomask prior to using the photomask to expose photoresist layers.

In some embodiments, photomasks that undergo periodic hydrocarboncontaminant removal operations according to the present disclosure havea service life of over 100× greater than photomasks that do not undergohydrocarbon contaminant removal according to the present disclosure.Proximity and critical dimension uniformity drift becomes unacceptablein some embodiments after about 800 exposures without performing thehydrocarbon removal operation (c-flash) of the present disclosure. Useof the hydrocarbon removal operation of the present disclosure increasesthe number exposures to about 17,000 between c-flash operations untilthe proximity and critical dimension uniformity drift becomesunacceptable in some embodiments, an increase in the number of exposuresof more than 20×. Because the c-flash operation may be performed up tofive times, the total lifetime of the photomask according to the methodsof the present disclosure is increased over 100× the lifetime ofphotomasks not undergoing the hydrocarbon removal operations of thepresent disclosure. Thus, the methods of the present disclosure improvesemiconductor device yield, and provide a more efficient semiconductordevice manufacturing process.

In some embodiments, the hydrocarbon contaminant removal operationaccording to the present disclosure substantially reduces or eliminatescritical dimension uniformity drift; substantially reduces or eliminatesproximity bias drift, and substantially reduces or eliminates whitespots on the photomask.

An embodiment of the disclosure is a method, including exposing aphotoresist coated substrate to radiation reflected off of a reflectivephotomask, or storing the reflective photomask for a period of timewithout using the reflective photomask in a photolithographic operation.Contamination forms on a surface of the reflective photomask during theexposing or storing. The reflective photomask having contamination on asurface thereof is placed in a plasma processing chamber after using thereflective photomask to expose the photoresist coated substrate or afterthe period of time. The reflective photomask having the contamination isplasma processed in the plasma processing chamber to remove thecontamination from the surface. The plasma includes oxygen plasma orhydrogen plasma. In an embodiment, the plasma processing chamber ismaintained at a pressure of 1 mtorr to 5 mtorr during the plasmaprocessing. In an embodiment, the contamination is a carbon-basedresidue. In an embodiment, the carbon-based residue includes ahydrocarbon. In an embodiment, the contamination is disposed on apattern in an absorber layer of the photomask. In an embodiment, oxygenis supplied to the plasma processing chamber at a flow rate of 10 sccmto 100 sccm. In an embodiment, oxygen is supplied to the plasmaprocessing chamber at a flow rate of 20 sccm to 50 sccm. In anembodiment, the method includes supplying chlorine to the plasmaprocessing chamber at a flow rate of 20 sccm to 100 sccm. In anembodiment, the method includes supplying nitrogen to the plasmaprocessing chamber at a flow rate of 10 sccm to 50 sccm. In anembodiment, hydrogen is supplied to the plasma processing chamber at aflow rate of 20 sccm to 100 sccm. In an embodiment, the method includessupplying helium or argon to the plasma processing chamber at flow rateof 60 sccm to 300 sccm. In an embodiment, a source power of the plasmaprocessing chamber during the plasma processing ranges from 100 W to1000 W. In an embodiment, a duration of the plasma processing rangesfrom 5 s to 100 s. In an embodiment, the method includes inspecting thereflective photomask to determine if the contamination is removed afterexposing the reflective photomask to the plasma.

Another embodiment of the disclosure is a method, including forming aphotomask, and using the photomask in a photolithographic process toform a photoresist pattern on a substrate. The photomask plasmaprocessed in a plasma processing chamber after using the photomask in aphotolithographic process to remove contamination from a surface of thephotomask. The plasma includes oxygen plasma or hydrogen plasma. In anembodiment, the forming a photomask includes operations of forming aMo/Si multilayer over a substrate, forming a capping layer over theMo/Si multilayer, forming an absorber layer over the capping layer,forming a hard mask layer over the absorber layer, and forming a firstphotoresist layer over the hard mask layer. In an embodiment, the methodincludes patterning the first photoresist layer to expose a portion ofthe hard mask layer, etching the exposed portion of the hard mask layerto expose a portion of the absorber layer, etching the exposed portionof the absorber layer to expose a portion of the capping layer, andremoving the hard mask layer to expose an upper surface of the absorberlayer. In an embodiment, the plasma processing chamber is maintained ata pressure of 1 mtorr to 5 mtorr during the plasma processing. In anembodiment, the contamination is a carbon-based residue. In anembodiment, the carbon-based residue includes a hydrocarbon. In anembodiment, the contamination is disposed on a pattern in an absorberlayer of the photomask. In an embodiment, oxygen is supplied to theplasma processing chamber at a flow rate of 10 sccm to 100 sccm. In anembodiment, oxygen is supplied to the plasma processing chamber at aflow rate of 20 sccm to 50 sccm. In an embodiment, the method includessupplying chlorine to the plasma processing chamber at a flow rate of 20sccm to 100 sccm. In an embodiment, the method includes supplyingnitrogen to the plasma processing chamber at a flow rate of 10 sccm to50 sccm. In an embodiment, hydrogen is supplied to the plasma processingchamber at a flow rate of 20 sccm to 100 sccm. In an embodiment, themethod includes supplying helium or argon to the plasma processingchamber at flow rate of 60 sccm to 300 sccm. In an embodiment, a sourcepower of the plasma processing chamber during the plasma processingranges from 100 W to 1000 W. In an embodiment, the duration of theplasma processing ranges from 5 s to 100 s.

Another embodiment of the disclosure is a method, including forming aphotomask, and storing the photomask in a photomask pod. The photomaskis plasma processed in a plasma processing chamber after storing thephotomask in the photomask pod to remove contamination from a surface ofthe photomask. The plasma includes oxygen plasma or hydrogen plasma. Inan embodiment, the forming a photomask includes operations of forming aMo/Si multilayer over a substrate, forming a capping layer over theMo/Si multilayer, forming an absorber layer over the capping layer,forming a hard mask layer over the absorber layer, and forming a firstphotoresist layer over the hard mask layer. In an embodiment, the methodincludes patterning the first photoresist layer to expose a portion ofthe hard mask layer, etching the exposed portion of the hard mask layerto expose a portion of the absorber layer, etching the exposed portionof the absorber layer to expose a portion of the capping layer, andremoving the hard mask layer to expose an upper surface of the absorberlayer. In an embodiment, the plasma processing chamber is maintained ata pressure of 1 mtorr to 5 mtorr during the plasma processing. In anembodiment, the contamination is a carbon-based residue. In anembodiment, the carbon-based residue includes a hydrocarbon. In anembodiment, the contamination is disposed on a pattern in an absorberlayer of the photomask. In an embodiment, oxygen is supplied to theplasma processing chamber at a flow rate of 10 sccm to 100 sccm. In anembodiment, oxygen is supplied to the plasma processing chamber at aflow rate of 20 sccm to 50 sccm. In an embodiment, the method includessupplying chlorine to the plasma processing chamber at a flow rate of 20sccm to 100 sccm. In an embodiment, the method includes supplyingnitrogen to the plasma processing chamber at a flow rate of 10 sccm to50 sccm. In an embodiment, hydrogen is supplied to the plasma processingchamber at a flow rate of 20 sccm to 100 sccm. In an embodiment, themethod includes supplying helium or argon to the plasma processingchamber at flow rate of 60 sccm to 300 sccm. In an embodiment, a sourcepower of the plasma processing chamber during the plasma processingranges from 100 W to 1000 W. In an embodiment, the duration of theplasma processing ranges from 5 s to 100 s.

Another embodiment of the disclosure is a method, including exposing aphotoresist coated substrate to actinic radiation reflected off of areflective photomask. The reflective photomask is placed in a chamberafter using the reflective photomask to expose the photoresist-coatedsubstrate. The reflective photomask is exposed to a plasma in thechamber to remove contamination from a surface of the reflectivephotomask. The plasma includes oxygen plasma or hydrogen plasma. In anembodiment, exposing a photoresist-coated substrate to actinic radiationcomprises performing a plurality of photoresist exposures to actinicradiation. In an embodiment, the plurality of photoresist exposuresranges from 100 to 2500. In an embodiment, the actinic radiation isextreme ultraviolet radiation. In an embodiment, the plasma furthercomprises chlorine, nitrogen, helium, argon, or combinations thereof.

Another embodiment of the disclosure is a method of reducing white spotdefects and critical dimension uniformity drift, including exposing aphotoresist coated substrate to actinic radiation reflected off of areflective photomask, or storing the reflective photomask for a periodof time without using the reflective photomask in a photolithographicoperation. The reflective photomask is placed in a chamber after usingthe reflective photomask to expose the photoresist-coated substrate orafter the period of time. After placing the reflective photomask in thechamber, a carbon-based residue contamination is removed from a surfaceof the reflective photomask using a plasma. In an embodiment, the plasmacomprises oxygen, hydrogen, argon, helium, chlorine, or nitrogen. In anembodiment, exposing a photoresist-coated substrate to actinic radiationcomprises performing a plurality of photoresist exposures to actinicradiation. In an embodiment, the plurality of photoresist exposuresranges from 100 to 2500. In an embodiment, the period of time is atleast 30 days. In an embodiment, the period of time is 30 days to 180days. In an embodiment, the actinic radiation is extreme ultravioletradiation. In an embodiment, the method includes inspecting thereflective photomask to determine whether the carbon-based residuecontamination is removed.

Another embodiment of the disclosure is a method, including determiningwhether a surface of a photomask is contaminated with a carbon-basedresidue. The photomask is place in a chamber when it is determined thesurface of the photomask is contaminated with the carbon-based residue.The photomask is exposed to a plasma in the chamber to remove thecarbon-based residue. The photomask is inspected to determine if thecarbon-based residue is removed after exposing the photomask to theplasma. In an embodiment, the method includes using the photomask toexpose a photoresist-coated substrate to extreme ultraviolet radiationafter determining the carbon-based residue is removed. In an embodiment,the plasma includes oxygen plasma or hydrogen plasma. In an embodiment,the chamber is maintained at a pressure of 1 mtorr to 5 mtorr during theexposing the photomask to a plasma. In an embodiment, the methodincludes supplying chlorine, nitrogen, helium, or argon to the chamberduring the exposing the photomask to a plasma. In an embodiment, theplasma is applied to the photomask at a power ranging from 100 W to 1000W. In an embodiment, the plasma is applied to the photomask for aduration time ranging from 5 s to 100 s.

The foregoing outlines features of several embodiments or examples sothat those skilled in the art may better understand the aspects of thepresent disclosure. Those skilled in the art should appreciate that theymay readily use the present disclosure as a basis for designing ormodifying other processes and structures for carrying out the samepurposes and/or achieving the same advantages of the embodiments orexamples introduced herein. Those skilled in the art should also realizethat such equivalent constructions do not depart from the spirit andscope of the present disclosure, and that they may make various changes,substitutions, and alterations herein without departing from the spiritand scope of the present disclosure.

What is claimed is:
 1. A method, comprising: exposing a photoresistcoated substrate to radiation reflected off of a reflective photomask,or storing the reflective photomask for a period of time without usingthe reflective photomask in a photolithographic operation, whereincontamination forms on a surface of the reflective photomask during theexposing or storing; placing the reflective photomask havingcontamination on a surface thereof in a plasma processing chamber afterusing the reflective photomask to expose the photoresist coatedsubstrate or after the period of time; and plasma processing thereflective photomask having the contamination in the plasma processingchamber to remove the contamination from the surface, wherein the plasmaincludes oxygen plasma or hydrogen plasma.
 2. The method according toclaim 1, wherein the plasma processing chamber is maintained at apressure of 1 mtorr to 5 mtorr during the plasma processing.
 3. Themethod according to claim 1, wherein the contamination is disposed on apattern in an absorber layer of the photomask.
 4. The method accordingto claim 1, wherein oxygen is supplied to the plasma processing chamberat a flow rate of 10 sccm to 100 sccm.
 5. The method according to claim1, further comprising supplying chlorine to the plasma processingchamber at a flow rate of 20 sccm to 100 sccm.
 6. The method accordingto claim 1, further comprising supplying nitrogen to the plasmaprocessing chamber at a flow rate of 10 sccm to 50 sccm.
 7. The methodaccording to claim 1, wherein hydrogen is supplied to the plasmaprocessing chamber at a flow rate of 20 sccm to 100 sccm.
 8. The methodaccording to claim 1, further comprising supplying helium or argon tothe plasma processing chamber at flow rate of 60 sccm to 300 sccm. 9.The method according to claim 1, wherein the source power of the plasmaprocessing chamber during the plasma processing ranges from 100 W to1000 W.
 10. The method according to claim 1, wherein the duration of theplasma processing ranges from 5 s to 100 s.
 11. A method, comprising,forming a photomask; using the photomask in a photolithographic processto form a photoresist pattern on a substrate; and plasma processing thephotomask in a plasma processing chamber after using the photomask in aphotolithographic process to remove contamination from a surface of thephotomask, wherein the plasma includes oxygen plasma or hydrogen plasma.12. The method according to claim 11, wherein the forming a photomaskincludes operations of: forming a Mo/Si multilayer over a substrate;forming a capping layer over the Mo/Si multilayer; forming an absorberlayer over the capping layer; forming a hard mask layer over theabsorber layer; and forming a first photoresist layer over the hard masklayer.
 13. The method according to claim 12, further comprising:patterning the first photoresist layer to expose a portion of the hardmask layer; etching the exposed portion of the hard mask layer to exposea portion of the absorber layer; etching the exposed portion of theabsorber layer to expose a portion of the capping layer; and removingthe hard mask layer to expose an upper surface of the absorber layer.14. The method according to claim 11, wherein the plasma processingchamber is maintained at a pressure of 1 mtorr to 5 mtorr during theplasma processing.
 15. The method according to claim 11, wherein oxygenis supplied to the plasma processing chamber at a flow rate of 10 sccmto 100 sccm.
 16. The method according to claim 11, further comprisingsupplying chlorine to the plasma processing chamber at a flow rate of 20sccm to 100 sccm, or supplying nitrogen to the plasma processing chamberat a flow rate of 10 sccm to 50 sccm.
 17. The method according to claim11, wherein hydrogen is supplied to the plasma processing chamber at aflow rate of 20 sccm to 100 sccm.
 18. The method according to claim 11,further comprising supplying helium or argon to the plasma processingchamber at flow rate of 60 sccm to 300 sccm.
 19. The method according toclaim 11, wherein the source power of the plasma processing chamberduring the plasma processing ranges from 100 W to 1000 W.
 20. A method,comprising, forming a photomask; storing the photomask in a photomaskpod; and plasma processing the photomask in a plasma processing chamberafter storing the photomask in the photomask pod to remove contaminationfrom a surface of the photomask, wherein the plasma includes oxygenplasma or hydrogen plasma.